Synthesis of poly[N-(3-ethoxypropyl)acrylamide] by ATRP in water and an exploration of the challenges of GPC-Based molecular weight characterization


YILDIZ M., ŞÖLENER M.

Polymer Bulletin, cilt.83, sa.1, 2026 (SCI-Expanded, Scopus) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 83 Sayı: 1
  • Basım Tarihi: 2026
  • Doi Numarası: 10.1007/s00289-025-06050-5
  • Dergi Adı: Polymer Bulletin
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Chemical Abstracts Core, Chimica, Compendex, INSPEC
  • Anahtar Kelimeler: ATRP, Characterization, GPC, N-(3-Ethoxypropyl)acrylamide, Thermoresponsive
  • Eskişehir Osmangazi Üniversitesi Adresli: Evet

Özet

N-(3-Ethoxypropyl)acrylamide was synthesized via a nucleophilic substitution reaction between acryloyl chloride and amines. Polymers of various molecular weights were synthesized by ATRP, which has not been extensively studied for N-(3-ethoxypropyl)acrylamide until recently. The molecular weight and structure of the products were determined based on GPC and 1H NMR analyses. ATRP reactions carried out in aqueous media achieved a polymer yield of 90% when a 1:1:3 ratio of the [I]/[CuBr]/[HMTETA] initiator–activator–ligand system was used. The polydispersity was less than 1.50, complying with one of the criteria for controlled polymerization. However, the Mn values estimated using 1H NMR analysis, which is known to have high accuracy in absolute molecular weight assessments, were high and inconsistent with the theoretical Mn values. Cross-checks were conducted using GPC equipment with varying eluent, solvent, and flow-rate configurations. Despite analyzing the same polymer, significant differences in the results were noted owing to variations in the GPC conditions. The Mn value of the poly[N-(3-ethoxypropyl)acrylamide] polymer, estimated as 35,200 g/mol using 1H NMR analysis, was measured to be 13,200 and 54,800 g/mol using GPCTHF and GPCDMF, respectively. The polydispersity values (Ɖ) were found to be 1.42 and 1.38, respectively. The LCST of the copolymer synthesized using the MPEG45-Br macroinitiator, was found to be 10 °C higher than those of the homopolymer of poly[N-(3-ethoxypropyl)acrylamide] and the triblock copolymer, synthesized using the PEG34-Br2 macroinitiator. Analysis of the particle size distribution data indicated that the copolymers showed a multi-peak distribution at temperatures below and immediately below the LCST, while aggregating at temperatures above the LCST.